Catalytic process for producing gas rich in hydrogen



Patented Feb. 20,. 1934 UNITED STATES PATENT OFFICE CATALYTIC PROCESSFOR PRODUCING GAS RICH IN HYDROGEN Garland H. B. Davis and James A.Franceway, Baton Rouge, La., assignors to Standard Oil DevelopmentCompany, a corporation of Delaware No Drawing. Application July 24, 1929Serial No. 380,753

12 Claims.

The present invention relates to the production of a gas rich in freehydrogen by reaction of hydrocarbons with steam and to a catalyst whichis particularly satisfactory for the process. The

invention will be fully understood from the following description:

The reaction of hydrocarbons either-gaseous or liquid of the paraffinseries with steam to produce hydrogen and carbon monoxide is well knownand a variety of catalysts have been discovered for use in the reaction.Heretofore, however, the most active catalysts have been characterizedby a lack of structural strength and tendency to shrink greatly involume after being in use for relatively short periods, so that tubesmust be continually refilled to prevent channelling and consequently animperfect contact. v

The present catalyst has none of the above disadvantageous qualities andis more rugged in commercial operation. In the manufacture of thiscatalyst certain metallic oxides such as nickel oxide,. or chromiumoxide,- are mixed with aluminum oxide and to the mixture phosphoric acidis added in quantity sufficient to permit the mass beingworked up into athick paste. While nickel or chromium oxide is preferred, it may bereplaced in whole or in 'part with oxides of cobalt or .manganese oriron and in the same manner the aluminum, may be replaced by otherrefractory oxides such as an oxide of earth metals such as thorium,zirconium and thallium and other metals of the third and earth metals ofthe fourth' group of the periodic system. Nickel and aluminum oxides arepreferred and the first is preferably in proportion fromabout to 70% byweight.

The phosphoric acid paste is baked dry for several hours at temperaturesabove 200 F. and preferably at about 225 F. The mass is then broken intolumps which are charged to the conversion chambers or retorts.

These catalysts may be suitably used for the production of hydrogen bypassing a gas rich in hydrocarbons and steam at a reaction temperatureover the catalyst disposed in a suitable reaction vessel.

As an example of the action and composition of these catalysts, thefollowing is typical. The

ingredients are powdered and mixed in the following proportions:

. HsPO4 5.7 pounds85%, Hal-O4 by weight This mixture is kneaded into athick paste and spread on trays or pans and heated for 20 hoursatapproximately 320 F. It is then packed into a tube and amixture' ofrefinery gas of the following composition is passed over it in admixture60 with steam in excess of about187% of that required theoretically toconvert the entering carbon to C0:

Percent CH4 43.1 60 CzHs 16.9 CsHs 7.7' C4H10 3.5 C5H12 2.4 Cal-I4 5.7CsHs 8.0 CiHs 5.0

100.0 Total unsaturates 18.7

The temperature during the conversion stage is about 1700'F., and thespace velocity of inlet gas is '75 volumes per volume of catalyst perhour. The exit gas has the following composltions:

- Percent CO2. 8.4 Unsaturates 0.0 CO 18.3

H2. 72.3 CH4 0.7

CzHe 0.0

The catalyst is of particular advantage when used with gases or liquidhydrocarbons containing substantial quantity of unsaturates. Butv it isalso of considerable advantage when used with no saturated'liquid orgaseous hydrocarbons since it is extremely hard and structurally strongand shows little or no appreciable shrinkage with long continued use.

The present invention is not to be limited by any theory of themechanism or action of the catalytic process nor to any specificoperation which may have been given for purely illustrative purposes butonly by the following claims in no which it is desired to claim allnovelty inherent in the process.

We claim:

1. A catalyst for the production of hydrogen from hydrocarbon and steamcomprising a mixture with phosphoric acid of an oxide of a metal of anatomic weight between 52 and 59 and an oxide of a metal selected fromthe group consisting of the metals of group III andthe earth metals ofgroup IV of the periodic system.

2. A catalyst for the production of hydrogen from hydrocarbon and steamcomprising a mixture with phosphoric acid of an oxide of a metal of anatomic weight between 52 and 59 and an oxide of a metal selected fromthe group consisting of aluminum, thorium, zirconium and thallium.

3. A catalyst for the production of hydrogen from hydrocarbon and steamcomprising a mixture with phosphoric acid of nickel oxide and an oxideof a metal selected from the group consisting of the metals of group IIIand the earth metals of group IV of the periodic system.

4. A catalyst for the production of hydrogen from hydrocarbon and steamcomprising a mixture with phosphoric acid of nickel oxide and aluminumoxide. 7

5. Catalyst according to claim 4 in which the nickel oxide is in aproportion of 30 to by weight. a

6. Process for the manufacture of a catalyst comprising kneading amixture of two metal oxides, the one of a metal with an atomic weightbetween 52 and 59, the other of a metal selected from the groupconsisting of the metals of group III and the earth metals of group IVof the periodic system, with concentrated phosphoric acid and baking themixture at a high temperature below the temperature of fusion of eitheroxide.

7. An improved process for producing a. gas rich in free hydrogen whichcomprises passing a gas rich in hydrocarbons and steam at a reactiontemperature over a catalyst comprised of a mixture with phosphoric acidof an oxide 01 a metal of an atomic weight between 52 and 59 and anoxide of a metal selected from the group consisting of the metals ofgroup III and the earth metals of group IV of the periodic system.

8. An improved process for producing a gas rich in free hydrogen whichcomprises passing a gas rich in hydrocarbons and steam at a reactiontemperature over a catalyst comprised of a mixture with phosphoric acidof an oxide of a metal of an atomic weight between 52 and 59 and anoxide of a metal selected from the group consisting of aluminum,thorium, zirconium and thallium.

9. An improved process for producing a gas rich in free hydrogen whichcomprises passing a gas rich in hydrocarbons and steam at a reactiontemperature over a catalyst prepared from a mixture with phosphoric acidof nickel oxide and aluminum oxide.

10. A catalyst for the production of hydrogen from hydrocarbons andsteam comprising a mixturewith phosphoric acid of an oxide of a metal ofan atomic weight between 52 and 59 and a refractory oxide.

11. An improved process for producing a gas rich in free hydrogen whichcomprises passing a gas rich in hydrocarbons and steam at a reactiontemperature over a catalyst prepared from a mixture with phosphoric acidof an oxide of ametal of an atomic weight between 52 and 59 and arefractory oxide.

12. An improved process for producing a gas rich in free hydrogen whichcomprises passing a gas rich in hydrocarbons and steam at a reactiontemperature over a catalyst comprising a mixture with phosphoric acid ofnickel oxide and a refractory oxide.

GARLAND H. B. DAVIS. JAMES A. FRANCEWAY.

